US3006926A - Production of cyclic ethers - Google Patents
Production of cyclic ethers Download PDFInfo
- Publication number
- US3006926A US3006926A US835835A US83583559A US3006926A US 3006926 A US3006926 A US 3006926A US 835835 A US835835 A US 835835A US 83583559 A US83583559 A US 83583559A US 3006926 A US3006926 A US 3006926A
- Authority
- US
- United States
- Prior art keywords
- diol
- sulfuric acid
- cyclic ethers
- distilling
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000004292 cyclic ethers Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000003518 caustics Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- RVGLUKRYMXEQAH-UHFFFAOYSA-N 3,3-dimethyloxetane Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 claims description 6
- -1 HYDROXYL GROUPS Chemical group 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- BBLDTXFLAHKYFJ-UHFFFAOYSA-N 2,2,5,5-tetramethyloxolane Chemical compound CC1(C)CCC(C)(C)O1 BBLDTXFLAHKYFJ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000002921 oxetanes Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZWNMRZQYWRLGMM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diol Chemical compound CC(C)(O)CCC(C)(C)O ZWNMRZQYWRLGMM-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- VVXQOMGRTXHFBZ-UHFFFAOYSA-N 3-ethyl-2-propyloxetane Chemical class CCCC1OCC1CC VVXQOMGRTXHFBZ-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 239000004358 Butane-1, 3-diol Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
Definitions
- cyclic ethers containing from two to five carbon atoms in the ether ring may be readily and economically produced by adding a mixture of the corresponding diol and sulfuric acid to a hot aqueous solution of a caustic alkali and distilling off the cyclic ether thereby produced.
- sulfuric acid to diol While the proportion of sulfuric acid to diol is not critical, it is preferred to use not greater than an equimolar quantity of concentrated sulfuric acid.
- concentration of acid also is not critical, the use of 96-98% being convenient and satisfactory.
- a sulfuric acid concentration of at least 90% is preferred.
- the yield of cyclic ether is in general higher when the concentration of the aqueous caustic alkali (sodium or potassium hydroxide) solution is maintained at least about 40%.
- oxetanes such as 2-methyl-, 3,3-dimethyl-, 3,3-diethyl-, 3-ethyl-3-n-butyl-, 2-n-propyl-3-ethyl-oxetanes made from butane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2-ethyl-2-butylpropane-1,3-diol and 2- ethyl-3-propylpropane-1,3-dio1, respectively.
- oxetanes such as 2-methyl-, 3,3-dimethyl-, 3,3-diethyl-, 3-ethyl-3-n-butyl-, 2-n-propyl-3-ethyl-oxetanes made from butane-1,3-diol, 2,2-dimethylpropane-1,3-diol,
- cyclic ethers which can be made by the method or the invention are tetrahydrofuran, 2,2,5,5- tetramethyltetrahydrofuran and tetrahydropyran, made from butane-1,4-diol, 2,5-dimethylhexane-2,5-diol and pentane-l,5-diol, respectively.
- cyclic ethers which can be made by the method of the invention are tetrahydrofuran, 2,2,5,5- tetramethyltetrahydrofuran and tetrahydropyran, made from butane-1,4-diol, 2,5-dimetl1y1hexane-2,5-diol and pentane-1,5-diol, respectively.
- the distillate about 120 ml., separates into two layers.
- the lower aqueous layer is separated and partially redistilled to recover the organic material and the material thus recovered is combined with the original organic layer, dried with calcium chloride and distilled, giving about gm. of 3,3-dimethyloxetane boiling between 79 and 83 C., which can be further purified by redistillation from calcium hydride to a boiling point of 79.2 to 80.3 C. at 756 mm. of mercury.
- Z-methyloxetane is obtained by sal-ting out the distillate with calcium chloride.
- a method of making cyclic ethers which comprises feeding a mixture of an alkanediol in which the hydroxyl groups are separated by a chain of from 2 to 5 carbon atoms and concentrated sulfuric acid into a hot aqueous solution of a caustic alkali and distilling ofi the cyclic ether thereby produced.
- a method of making oxetanes which comprises feeding a mixture of an alkane-1,3-diol and concentrated sulfuric acid into a hot aqueous solution of a caustic alkali and distilling off the cyclic ether thereby produced.
Description
United States York No Drawing. Filed Aug. 25, 1959, Ser. No. 835,835 4 Claims. (Cl. 260-333) This invention relates to a novel method of preparing cyclic ethers.
We have found that cyclic ethers containing from two to five carbon atoms in the ether ring may be readily and economically produced by adding a mixture of the corresponding diol and sulfuric acid to a hot aqueous solution of a caustic alkali and distilling off the cyclic ether thereby produced.
While the proportion of sulfuric acid to diol is not critical, it is preferred to use not greater than an equimolar quantity of concentrated sulfuric acid. The concentration of acid also is not critical, the use of 96-98% being convenient and satisfactory. A sulfuric acid concentration of at least 90% is preferred.
The yield of cyclic ether is in general higher when the concentration of the aqueous caustic alkali (sodium or potassium hydroxide) solution is maintained at least about 40%.
While the method is useful in the preparation of cyclic ethers containing from two to five carbon atoms in the ether ring, it is particularly useful for the production of oxetanes, such as 2-methyl-, 3,3-dimethyl-, 3,3-diethyl-, 3-ethyl-3-n-butyl-, 2-n-propyl-3-ethyl-oxetanes made from butane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2-ethyl-2-butylpropane-1,3-diol and 2- ethyl-3-propylpropane-1,3-dio1, respectively.
Other typical cyclic ethers which can be made by the method or the invention are tetrahydrofuran, 2,2,5,5- tetramethyltetrahydrofuran and tetrahydropyran, made from butane-1,4-diol, 2,5-dimethylhexane-2,5-diol and pentane-l,5-diol, respectively.
Other typical cyclic ethers which can be made by the method of the invention are tetrahydrofuran, 2,2,5,5- tetramethyltetrahydrofuran and tetrahydropyran, made from butane-1,4-diol, 2,5-dimetl1y1hexane-2,5-diol and pentane-1,5-diol, respectively.
The following examples are illustrative of the principles of the invention:
3,3-dimethyloxetane 111 ml. of 96% sulfuric acid are added to 208 gm. of
2 neopentylglycol (2,2-dimethylpropaue-1,3-diol) and the mixture is stirred giving a very viscous solution. A solution of 240 gm. of sodium hydroxide in 200 ml. of water is brought to the boiling point in a 1 liter flask equipped with a stirrer, dropping funnel and distilling head. The glycol solution is added from the dropping funnel at such a rate as to maintain boiling. The glycol solution may be warmed to reduce the viscosity and maintain an adequate rate of flow.
The distillate, about 120 ml., separates into two layers. The lower aqueous layer is separated and partially redistilled to recover the organic material and the material thus recovered is combined with the original organic layer, dried with calcium chloride and distilled, giving about gm. of 3,3-dimethyloxetane boiling between 79 and 83 C., which can be further purified by redistillation from calcium hydride to a boiling point of 79.2 to 80.3 C. at 756 mm. of mercury.
Z-methyloxetane In the manner described in the foregoing example, gm. of 1,3-butyleneglycol dissolved in 55.5 ml. of sulfuric acid are added to a boiling solution of 240 gm. of sodium hydroxide in 250 ml. of water.
About 15 to 20 gm. of Z-methyloxetane is obtained by sal-ting out the distillate with calcium chloride.
We claim:
1. A method of making cyclic ethers which comprises feeding a mixture of an alkanediol in which the hydroxyl groups are separated by a chain of from 2 to 5 carbon atoms and concentrated sulfuric acid into a hot aqueous solution of a caustic alkali and distilling ofi the cyclic ether thereby produced.
2. A method of making oxetanes which comprises feeding a mixture of an alkane-1,3-diol and concentrated sulfuric acid into a hot aqueous solution of a caustic alkali and distilling off the cyclic ether thereby produced.
3. The method of making 3,3-dimethyloxetane which comprises feeding a mixture of 2,2-dirnethylpropane-L3- diol and concentrated sulfuric acid into a hot aqueous solution of a caustic alkali and distilling oil the 3,3-dimethyloxet-ane thereby produced.
4. The method of making Z-methyloxetane which comprises feeding a mixture of 1,3 butyleneglycol and concentrated sulfuric acid into a hot aqueous solution of a caustic alkali and distilling off the Z-methyloxetane thereby produced.
No references cited.
Claims (2)
1. A METHOD OF MAKING CYCLIC ETHERS WHICH COMPRISES FEEDING A MIXTURE OF AN ALKANEDIOL IN WHICH THE HYDROXYL GROUPS ARE SEPARATED BY A CHAIN OF FROM 2 TO 5 CARBON ATOMS AND CONCENTRATED SULFURIC ACID INTO A HOT AQUEOUS SOLUTION OF A CAUSTIC ALKALI AND DISTILLING OFF THE CYCLIC ETHER THEREBY PRODUCED.
3. THE METHOD OF MAKING 3,3-DIMETHYLOXETANE WHICH COMPRISES FEEDING A MIXTURE OF 2,2-DIMETHYLPROPANE-1,3DIOL AND CONCENTRATED SULFURIC ACID INTO A HOT AQUEOUS SOLUTION OF A CAUSTIC ALKALI AND DISTILLING OFF THE 3,3-DIMETHYLOXETANE THEREBY PRODUCED.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US835835A US3006926A (en) | 1959-08-25 | 1959-08-25 | Production of cyclic ethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US835835A US3006926A (en) | 1959-08-25 | 1959-08-25 | Production of cyclic ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3006926A true US3006926A (en) | 1961-10-31 |
Family
ID=25270594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US835835A Expired - Lifetime US3006926A (en) | 1959-08-25 | 1959-08-25 | Production of cyclic ethers |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3006926A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3153056A (en) * | 1961-12-01 | 1964-10-13 | Olin Mathieson | Organoboron cyclic ethers |
| US3164610A (en) * | 1962-02-16 | 1965-01-05 | Minnesota Mining & Mfg | Fluorinated oxetanes |
| US3278554A (en) * | 1961-10-11 | 1966-10-11 | Ciba Ltd | Esters containing more than one oxetane group |
| US5081268A (en) * | 1990-08-06 | 1992-01-14 | Arco Chemical Technology, Inc. | Process for the preparation of oxetanes from 1,3-glycol monosulfates |
| US5659089A (en) * | 1996-05-22 | 1997-08-19 | Arco Chemical Technology, L.P. | Process for making poly(2-methyl-1,3-propanediol) |
-
1959
- 1959-08-25 US US835835A patent/US3006926A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3278554A (en) * | 1961-10-11 | 1966-10-11 | Ciba Ltd | Esters containing more than one oxetane group |
| US3153056A (en) * | 1961-12-01 | 1964-10-13 | Olin Mathieson | Organoboron cyclic ethers |
| US3164610A (en) * | 1962-02-16 | 1965-01-05 | Minnesota Mining & Mfg | Fluorinated oxetanes |
| US5081268A (en) * | 1990-08-06 | 1992-01-14 | Arco Chemical Technology, Inc. | Process for the preparation of oxetanes from 1,3-glycol monosulfates |
| US5659089A (en) * | 1996-05-22 | 1997-08-19 | Arco Chemical Technology, L.P. | Process for making poly(2-methyl-1,3-propanediol) |
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